Redetermined structure of 4,4
000-bi-pyridine–1,4-phenylenediacetic acid (1/
1) co-crystal
Rima Paul and Sanchay Jyoti Bora*
Department of Chemistry, Pandu College, Guwahati-781 012, Assam, India. *Correspondence e-mail: sanchay.bora@gmail.com
Received 14 September 2015; accepted 19 September 2015
Edited by W. T. A. Harrison, University of Aberdeen, Scotland
The asymmetric unit of the title 1:1 co-crystal, C10H8N2C10H10O4, consists of one half-molecule each of
4,40-bipyridine and 1,4-phenylenediacetic acid: the complete molecules are generated by crystallographic inversion centres. The dihedral angle between the –CO2H group and the
benzene ring in the diacid is 73.02 (7). In the crystal, the components are linked by O—H N hydrogen bonds, generating [121] chains of alternating amine and carboxylic acid molecules. The chains are cross-linked by C—H O interactions. This structure was previously incorrectly described as a (C10H10N2)2+(C10H8O4)2 molecular salt [Jia et al.(2009).Acta Cryst.E65, o2490–o2490].
Keywords:crystal structure; co-crystal; supramolecular interaction; hydrogen bonding.
CCDC reference:1423417
1. Related literature
For the previous erroneous report of this structure as a mol-ecular salt, see: Jia et al. (2009). For hydrogen-bonded co-crystals, see: Stahly (2009); Kavuru et al. (2010). For phar-maceutical co-crystals, see: Childs et al. (2009); Walsh et al. (2003). For a similar structure, see: Chinnakaliet al.(1999).
2. Experimental
2.1. Crystal data C10H8N2C10H10O4 Mr= 350.36 Triclinic,P1
a= 4.5577 (5) A˚
b= 6.9806 (8) A˚
c= 13.7995 (15) A˚
= 99.508 (6)
= 94.297 (6)
= 97.643 (7) V= 427.05 (8) A˚3 Z= 1
MoKradiation
= 0.10 mm1
T= 296 K
0.200.170.13 mm
2.2. Data collection Bruker SMART CCD
diffractometer 8581 measured reflections
2405 independent reflections 1876 reflections withI> 2(I)
Rint= 0.028
2.3. Refinement
R[F2> 2(F2)] = 0.041
wR(F2) = 0.123 S= 1.05 2405 reflections
155 parameters
All H-atom parameters refined
max= 0.19 e A˚3
min=0.16 e A˚
3
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O1—H9 N1i 1.02 (2) 1.62 (2) 2.6373 (13) 176 (2) C7—H6 O2ii
0.954 (16) 2.504 (16) 3.4196 (16) 160.8 (11) C9—H7 O2iii
1.00 (2) 2.45 (2) 3.4205 (18) 162.2 (16)
Symmetry codes: (i)xþ2;yþ1;z; (ii)x;y;zþ1; (iii)xþ1;yþ2;z.
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows(Farrugia, 2012); software used to prepare material for publication:SHELXL97.
Acknowledgements
Financial support from the Department of Science & Tech-nology, India (under FASTRACK Grant No. SB/FT/CS-047/ 2013) is gratefully acknowledged. The authors also thank the USIC, Gauhati University, Guwahati (India), for providing the X-ray diffraction data.
Supporting information for this paper is available from the IUCr electronic archives (Reference: HB7506).
References
Bruker (2004).SMARTandSAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Childs, S. L. & Zaworotko, M. J. (2009).Cryst. Growth Des.9, 4208–4211. Chinnakali, K., Fun, H.-K., Goswami, S., Mahapatra, A. K. & Nigam, G. D.
(1999).Acta Cryst.C55, 399–401.
Farrugia, L. J. (2012).J. Appl. Cryst.45, 849–854.
Jia, M., Liu, X., Miao, J., Xiong, W. & Chen, Z. (2009).Acta Cryst.E65, o2490.
data reports
Acta Cryst.(2015).E71, o799–o800 doi:10.1107/S2056989015017569 Paul and Bora
o799
Kavuru, P., Aboarayes, D., Arora, K. K., Clarke, H. D., Kennedy, A., Marshall, L., Ong, T. T., Perman, J., Pujari, T., Wojtas, Ł., Łukasz, & Zaworotko, M. J. (2010).Cryst. Growth Des.10, 3568–3584.
Sheldrick, G. M. (2008).Acta Cryst.A64, 112–122.
Stahly, G. P. (2009).Cryst. Growth Des.9, 4212–4229.
supporting information
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Acta Cryst. (2015). E71, o799–o800
supporting information
Acta Cryst. (2015). E71, o799–o800 [doi:10.1107/S2056989015017569]
Redetermined structure of 4,4
′
-bipyridine
–
1,4-phenylenediacetic acid (1/1)
co-crystal
Rima Paul and Sanchay Jyoti Bora
S1. Comment
Co-crystals represent a class of materials which contain two or more discrete molecular entities held together via non-covalent or supramolecular interactions in the crystal lattice (Stahly, 2009). Due to their robust and directional nature,
hydrogen bonds are extensively used as a tool to shape the structure of co-crystals (Kavuru et al., 2010). In this context, hydrogen bonds of varying strengths may be employed, ranging from strong O—H···O/N to weak C—H···π interactions. The resulting crystal structures can generate diverse physical and chemical properties such as solubility and stability that
differ from the properties of the individual components. Crystal engineering plays an important role in the formation of
co-crystals of desired properties so that they can find their applications in pharmaceutical industries (Childs et al., 2009 and Walsh et al., 2003). Herein, we report the supramolecular architecture of 1,4-phenylenediacetic acid and 4,4′-bi-pyridine co-crystal formed via O—H···N hydrogen bridges and C—H···π interactions.
The title compound can be prepared under hydrothermal condition using a mixture of 1,4-phenylenediacetic acid and
4,4′-bipyridine (1:1) in water. The acetic acid moiety involving C1, C2, O1 and O2 in 1,4-phenylenediacetic acid
molecule makes dihedral angles of 73.04 (4)° and 2.06 (1)° with the phenyl and pyridyl ring planes respectively. These
values are very close to those reported by Chinnakali et al. (1999). The dihedral angle between phenyl and planar pyridyl rings of 4,4′-bipyridine is found to be 73.21 (4)°. In the crystal lattice, the molecules are linked with one another through
O1—H9···N1 hydrogen bonds with O···N distance of 2.637 (1) Å that extends in one direction leading to a
supra-molecular chain like structure. These zig-zag 1D chains are further connected via C—H···O bridges (C7—H6···O2 and C9
—H7···O2 with C···O distances of 2.50 (1) Å and 2.45 (2) Å respectively) giving rise to a 2D layered structure in the
solid state. In graph set notations (Bernstain et al., 1995), such 1D chains can be described as C22(20) where the
subscripts and superscripts are the number of hydrogen bond donors and acceptors respectively. There are certain
hydrogen bonded rings of descriptors R12(7), R44(16) and R44(30) which have periodic repetitions throughout the crystal
lattice. The adjacent layers are stacked in nearly parallel fashion by means of weak C—H···π interactions (C···π distance = 3.838 Å) between the methylene C—H and phenyl ring–π systems. These weak intermolecular forces together with the strong hydrogen bonds form the overall 3D supramolecular architecture.
?
S2. Synthesis and crystallization
A mixture of 1,4-phenylenediacetic acid (1 mmol, 0.194 g) and 4,4?-bipyridine (1 mmol, 0.156 g) in water (10 ml) were
placed in a 23 ml Teflon lined stainless steel reaction vessel. It was then heated to 393K for 24 hours at a heating rate of
5K min-1. On overnight standing, rectangular block shaped colourless crystals were obtained. The crystals were then
S3. Refinement
Structure determination work was done using the WinGX platform (Farrugia, 2012). All the hydrogen atoms were located in difference Fourier maps and refined with isotropic atomic displacement parameters. No restraints were applied for any
[image:4.610.133.471.139.325.2]other parameter during structure refinement.
Figure 1
[image:4.610.134.475.365.495.2]The molecular structure of (I) showing 50% probability displacement ellipsoids.
Figure 2
A view of the O—H···N, C—H···O and C—H···π interactions observed in the crystal structure of the title compound.
4,4′-Bipyridine–1,4-phenylenediacetic acid (1/1)
Crystal data
C10H8N2·C10H10O4
Mr = 350.36
Triclinic, P1
a = 4.5577 (5) Å
b = 6.9806 (8) Å
c = 13.7995 (15) Å
α = 99.508 (6)°
β = 94.297 (6)°
γ = 97.643 (7)°
V = 427.05 (8) Å3
Z = 1
F(000) = 184
Dx = 1.362 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
µ = 0.10 mm−1
T = 296 K
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Acta Cryst. (2015). E71, o799–o800
Data collection
Bruker SMART CCD diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
phi and ω scans
8581 measured reflections 2405 independent reflections
1876 reflections with I > 2σ(I)
Rint = 0.028
θmax = 29.8°, θmin = 3.0°
h = −6→6
k = −9→9
l = −19→19
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.041
wR(F2) = 0.123
S = 1.05 2405 reflections 155 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
All H-atom parameters refined
w = 1/[σ2(F
o2) + (0.0605P)2 + 0.0515P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.19 e Å−3
Δρmin = −0.16 e Å−3
Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.061 (11)
Special details
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is
used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.8197 (2) 0.45294 (13) −0.18830 (6) 0.0541 (3)
C1 0.7209 (2) 0.60720 (15) −0.21279 (8) 0.0408 (3)
C2 0.5619 (3) 0.71533 (19) −0.13310 (10) 0.0490 (3)
C3 0.7850 (2) 0.86342 (15) −0.06291 (8) 0.0400 (3)
C4 0.9459 (3) 0.80852 (16) 0.01476 (9) 0.0454 (3)
C5 0.8422 (3) 1.05717 (17) −0.07687 (8) 0.0446 (3)
O2 0.7616 (3) 0.66207 (15) −0.28973 (7) 0.0675 (3)
N1 0.8832 (2) 0.73182 (15) 0.32203 (7) 0.0476 (3)
C6 0.8316 (3) 0.67172 (18) 0.40629 (9) 0.0517 (3)
C7 0.6844 (3) 0.77149 (18) 0.47798 (9) 0.0487 (3)
C8 0.5796 (2) 0.94340 (15) 0.46266 (7) 0.0376 (2)
C10 0.7840 (3) 0.8964 (2) 0.30711 (10) 0.0566 (3)
C9 0.6326 (3) 1.00451 (19) 0.37423 (9) 0.0532 (3)
H9 0.927 (5) 0.382 (3) −0.2421 (15) 0.104 (7)*
H4 0.731 (3) 1.100 (2) −0.1302 (11) 0.055 (4)*
H6 0.660 (3) 0.722 (2) 0.5378 (12) 0.067 (4)*
H1 0.462 (4) 0.621 (2) −0.0977 (12) 0.065 (4)*
H8 0.822 (4) 0.935 (2) 0.2459 (13) 0.073 (5)*
H7 0.560 (4) 1.122 (3) 0.3533 (13) 0.081 (5)*
H2 0.412 (4) 0.787 (3) −0.1669 (12) 0.071 (5)*
H5 0.902 (4) 0.551 (3) 0.4159 (12) 0.071 (4)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0764 (6) 0.0483 (5) 0.0463 (5) 0.0272 (4) 0.0173 (4) 0.0141 (4) C1 0.0449 (6) 0.0370 (5) 0.0403 (5) 0.0071 (4) 0.0035 (4) 0.0055 (4) C2 0.0434 (6) 0.0489 (6) 0.0549 (7) 0.0115 (5) 0.0119 (5) 0.0025 (5) C3 0.0431 (5) 0.0405 (5) 0.0396 (5) 0.0148 (4) 0.0163 (4) 0.0046 (4) C4 0.0580 (7) 0.0363 (5) 0.0467 (6) 0.0141 (5) 0.0146 (5) 0.0116 (4) C5 0.0545 (7) 0.0452 (6) 0.0394 (5) 0.0184 (5) 0.0097 (5) 0.0116 (4) O2 0.1023 (8) 0.0630 (6) 0.0502 (5) 0.0351 (6) 0.0215 (5) 0.0232 (4) N1 0.0507 (6) 0.0478 (5) 0.0450 (5) 0.0158 (4) 0.0075 (4) 0.0023 (4) C6 0.0643 (8) 0.0439 (6) 0.0511 (7) 0.0221 (6) 0.0096 (6) 0.0075 (5) C7 0.0631 (7) 0.0441 (6) 0.0443 (6) 0.0189 (5) 0.0116 (5) 0.0117 (5) C8 0.0370 (5) 0.0374 (5) 0.0379 (5) 0.0073 (4) 0.0026 (4) 0.0045 (4) C10 0.0714 (9) 0.0614 (8) 0.0466 (7) 0.0285 (6) 0.0200 (6) 0.0159 (6) C9 0.0691 (8) 0.0515 (7) 0.0490 (6) 0.0284 (6) 0.0181 (6) 0.0166 (5)
Geometric parameters (Å, º)
O1—C1 1.3051 (13) C5—H4 0.972 (14)
O1—H9 1.02 (2) N1—C6 1.3264 (16)
C1—O2 1.2056 (14) N1—C10 1.3301 (16)
C1—C2 1.5147 (16) C6—C7 1.3820 (17)
C2—C3 1.5108 (17) C6—H5 0.964 (17)
C2—H1 0.970 (16) C7—C8 1.3906 (15)
C2—H2 1.027 (17) C7—H6 0.955 (16)
C3—C4 1.3877 (16) C8—C9 1.3850 (16)
C3—C5 1.3908 (15) C8—C8ii 1.486 (2)
C4—C5i 1.3844 (18) C10—C9 1.3810 (17)
C4—H3 0.961 (15) C10—H8 0.950 (18)
C5—C4i 1.3844 (18) C9—H7 0.998 (19)
C1—O1—H9 112.6 (12) C3—C5—H4 120.1 (8)
O2—C1—O1 123.26 (10) C6—N1—C10 117.10 (10)
O2—C1—C2 123.39 (11) N1—C6—C7 123.47 (11)
O1—C1—C2 113.30 (10) N1—C6—H5 116.3 (10)
C3—C2—C1 109.58 (9) C7—C6—H5 120.2 (10)
C3—C2—H1 110.0 (9) C6—C7—C8 119.66 (11)
C1—C2—H1 108.9 (10) C6—C7—H6 119.0 (10)
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C1—C2—H2 107.7 (9) C9—C8—C7 116.53 (10)
H1—C2—H2 111.2 (13) C9—C8—C8ii 121.59 (12)
C4—C3—C5 118.28 (11) C7—C8—C8ii 121.88 (12)
C4—C3—C2 121.06 (10) N1—C10—C9 123.35 (12)
C5—C3—C2 120.61 (10) N1—C10—H8 115.3 (10)
C5i—C4—C3 120.99 (10) C9—C10—H8 121.3 (10)
C5i—C4—H3 119.3 (9) C10—C9—C8 119.89 (11)
C3—C4—H3 119.7 (9) C10—C9—H7 116.0 (11)
C4i—C5—C3 120.73 (11) C8—C9—H7 124.1 (11)
C4i—C5—H4 119.2 (8)
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O1—H9···N1iii 1.02 (2) 1.62 (2) 2.6373 (13) 176 (2)
C7—H6···O2iv 0.954 (16) 2.504 (16) 3.4196 (16) 160.8 (11)
C9—H7···O2v 1.00 (2) 2.45 (2) 3.4205 (18) 162.2 (16)